Refrigerant and method of making



Patented June 24, 1947 I U-N lT'ED- STATES PATENT F FlCE No Drawing. Application June 1, 1945; Serial No. 597,163

The present invention relates to an improvement of water ice as a refrigerant and method of making the same. This applicationis a continuation in part of my co-pending. application 442,236 filed May 8, 1942, emphasizing, thesalient features disclosed, therein. It is known in the art to hydrate Dry Ice by addition of small proportions of moisture tothe liquefiedgas during evaporation thereof. 2

It is also. known to use a combination of Dry Ice and water ice as a refrigerant whereby discrete portions of Dry Ice are associated with water ice such as by using proportionately large 5 Claims. (Cl. 252-457) blocks of, Dry 'Ice placed on top; of; a layer of ordinary water ice andeven. to. drill: holes in a block of ordinary ice and fill-the same with Dry Ice so that such product. wouldconsist of ordinary water ice blocks having inserted therein several discrete tubes or holes filled with pure DryIce.

It is also known to add. ordinary salts toice to form-an ice salt mixture whereby the ice ab.- sorbs some salt forming a salt solution having: a freezing point lower than waterinproportion to the salt content.

According to the present invention a substantially homogeneous mixture of Water icein major proportions and-carbon dioxide ice inminor proportions isformed by intimately associating the two ices such as by grinding the two different ices together using a major proportion of ordinary water ice and a minor proportion preferably 10% or less:of Dry Ice. But. it will be understood that a.significant:proportiomof:carbon' dioxide at least 0. 1% is always: used; such proportions beingun derstood to be critically sufficient tolproyide'Dry Ice to be absorbed in the surface of ground water ice.

Carbon dioxide at normal temperatures issaagas Whichaccording-to.the standardzphysical. chemical" laws will dissolve in other substances such as liquids in directproportion'to the;pressure:exer.ted

thereon. Also, according to. standard physical chemical laws, the quantity that will dissolve-is inversely proportional tothe temperature and therefore will increase as the temperature is lowered.

One method of the present invention favors increased'solutionof the carbon dioxide in Water ice according to both of theselaws in that-ordinary water ice'is ground-in the presence-eta minor quantity of Dry Ice. Grindinginvolves exertion of disruptive pressureandattritionupon both ices. Such pressureonordinary ice, while breaking the crystal structure into small fragments, would tend: to: liquefy; and form. a. surface-11111111 thereon of liquid; Simultaneously applied dis-- ruptive pressure on the Dry Ice in such grinding operation would tend to form solid CO2 particles and some CO2 gas orliquid. Since both ices are simultaneously ground much of the C02 is absorbedby the ordinary ice forming a surface film of dissolved, absorbed or coated ordinary icewith the Dry Ice. The resultant product is essentially waterice supercooled by contact with Dry Ice and having a substantial C02 content absorbed and dissolved in the surface thereof togive an ice-salt'effect of depressed melting point. Also if more Dry Ice is used' than is absorbed,- as is often the case in" a commercial grinding'or crushing operation, there will be present some unabsorbed free Dry Ice.

Ordinary Dry Ice associated'butundissolved or unabsorbediin the waterice will-exhibit-its nor mal properties of melting and vaporizing at'the extreme low temperature of 1l2 FE and the waterice will thereafter give up its normal sensible heat rapidly warming to 32 F; where it begins to melt giving up its heato f'fusion.

Howeverthe solidCOz of the present'invention which hasbeen. absorbed inthe. surface of the water ice will exhibit the properties therewith of an ice-salt mixture causingboth'the icean'd C02.

tion of. CO2 therein will be. reduced, resulting in" a. progressively higher. melting point of the, remaining ice mixture. Thusthe CO2 absorbed 3 water. ice will melt over a range. of meltingjpoints. intermediate that of ordinary water ice and-Dry Ice, and both iceshave been causedthereby to give up. some. oftheir. heats offusion at an intermediate temperature which can be controlled by the-quantity of Dry Ice absorbed by. the ordinary ice-and thus the bulkof the Dry Ice is caused to give up its refrigerating value.at.a-temperature above. its: normal vaporizing. temperature i. e., above 1 12 F.

Thus .it willbe appreciated that it is aprimary object'to associate the ices so that an intermediate melting composition is obtained wherein both ices contribute refrigerating. value. It isanobject to practically absorb as much of the CQziCe. 'in the water ice as possible and this will be in the range of 0.1 to 10% of the water ice. However; in a commercialgrinding: or crushing: all of the Dry'Ice, will not be absorbedrand some Dry Ice: willzremain, depending. on. thereificiencyof, the grinding or other-method of association. The.

excess free Dry Ice, unabsorbed merely has the effect of ordinary Dry Ice tending to hold the temperature of the mixture down to the normal vaporizing temperature of pure Dry Ice for a period of time depending on how much is present.

For example, if water ice and Dry Ice were mixed-so as to provide a considerable excess of Dry Ice in a ratio of /3 of water ice and /3 Dry Ice, by volume, the mixture would last 2% hours in a sawdust insulated box before the temperature begins to rise appreciably above 'l5 F.

Thus the invention will be understood to relate to ice containing a small amount of CO2, usually less than 10% of the order of .1 to 10%. Quantities such as .1% to 2% are preferably used for ordinary refrigeration ice and .1 to 5% is preferred quantity range where the ice is to be used for carbonated beverages.

The product, therefore, is essentially ice supercooled when made substantially below the normal freezing point and maintained as such for refrigerating purposes by a small content of solid or dissolved CO2. It is ice, often abnormally cold, but otherwise useful as a refrigerant for most purposes for which ordinary ice is used except that it may be colder and will last longer.

The product is to be distinguished from solid CO2 which normally may contain a small quantity of ice as impurity. Also it is distinguished from simple mixtures of solid CO2 and ice wherein the said carbon dioxide is in greater proportions, which have not the utility of ordinary ice because they fume and maintain too drastic subfreezing conditions. Such refrigerants freeze foods which may be undesirable and useless in beverages.

The present, refrigerant, containing less than of 002 when associated with food, quickly chills the same and is itself warmed in the process to substantially the ordinary freezing temperature of water. Therefore,.it lasts longer without drastically superfreezing the foods with which it comes in contact. For example, ice cream is solidified quickly therewith but not frozen so hard as to be unpalatable. Similarly, fruits, vegetables, milk, meats and fish are quickly chilled therewith but are not frozen as is usual with solid CO2 or mixtures of solid CO2 in great quantities with ice.

An ideal use for this type of ice, which may be used in the form of cracked ice, snow or cubes, is in beverages of the carbonated type. There is present in the ice a small quantity of CO2 partially to carbonate the water so that ordinary water may be added to form carbonated water. It tends to overcome the disadvantage of ordinary ice which dilutes and weakens carbonated water. This disadvantage is so pronounced that ordinary ice is useless in some carbonated beverages because it dilutes and flattens it; for example, ordinary ice cannot be added to beer, ale or carbonated wines such as champagne. The ice of the present invention, when added to beverages, quickly chills the same and replaces the CO2 normally lost in the ordinary addition of ice to carbonated water. At the same time, there is not sufiicient CO2 in the ice to give an undue ebullition of CO2 gas as would be the case when using substantially greater proportions than 10% of CO2.

with 90% ice by weight to give a composite supercooled cracked ice or snow. During the grinding period a portionas much or more than 5% of COz-may be lost in the heat exchange in supercooling the ice and in the heat of grinding so that the super-cooled ice product may contain less than 10% of solid CO2 and, as stated above, for most purposes 5% of CO2 is adequate.

The super-cooled cracked ice or snow product may be used as such or compressed into cakes, cubes, balls, boulettes, or pillows, large blocks or any other desirable shape or size depending on the use for which they are intended herein included under the term bn'quets.

Example II Add solid or liquid CO2 to water in proportions to freeze the water, cool to sub-freezing temperatures and allow a'few per cent of CO2 to remain. Here, again, 10% of solid or liquid CO2 will suffice. When using this method, the product may be formed into porous lumps of any desired shape which may be, of course, further compacted or cracked as desired.

Example III Dissolve carbon dioxide gas in water under super-atmospheric pressure and in the presence of an excess of 1 to 3% of the gas. The system is then super-cooled by any refrigerating means until the water and at least part of the CO2 is frozen. The product formed in this manner may be a clear and transparent product if desired, but it may be further ground, cracked or used in any manner.

Example IV A snow is formed by grinding ordinary ice with solid CO2 in the proportion of 5% of solid CO2 to 95% of ice, as in Example 1.

Example V Carbon dioxide snow'is mixed in the propor tions of 10% carbon dioxide with of ordinary snow or cracked ice. A super-cooled granular snow or cracked ice is obtained containing less than 10% of CO2.

Example VI Ice as formed in Examples I to V is added to .various beverages which may or may not already contain CO2, such as orange juice, colas, beer, wine or champagne, lemonade, fruit punch, etc. etc.

Examples VII A block of ice formed by any of the examples above, is placed in an ice refrigerator and found to maintain foods in a cold condition for a substantial period.

Example VIII Ice cream, fresh vegetables, fish and meats packed in snow or cracked ice of Examples I to V are found to be well frozen for a longer period than when packed in ordinary ice and are not as hard as when refrigerated with only solid carbon dioxide.

Example IX Example X The ices formed in'Examples 1 to 5 are treated by addition thereto of comestible flavoring, the whole mass agglomerating and freezing to form a comestible ice of various flavors. Such flavors as sweet syrups of fruit or chocolate may be used.

As used herein, the term ice refers to frozen water. Solid CO2 or Dry Ice is frozen carbon dioxide gas.

Various modifications will occur to those skilled in the art, the examples given above being for purposes of clarification and not intended to be limiting except as defined in the claims.

Iclaim:

1. Method of forming a solid refrigerant comprising homogeneously mixing with attrition a major portion of Water ice and a minor proportion of solid C02.

2. Method of forming a, solid refrigerant comprising grinding a major proportion of solid Water ice with a minor proportion of solid C02.

3. Method of forming a solid refrigerant comprising grinding solid water ice with a smaller proportion, about 0.1 to 10 per cent thereof, of solid C02.

4. Method as defined in claim 2 wherein the resulting refrigerant is formed into briquets.

SOL B. WICZER.

' REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,757,383 Pankney May 6, 1930 1,927,175 Josephson Sept. 19, 1933 2,014,245 Donahoe Sept. 10, 1935 

